Hydantoin derivatives of cyano-substituted chrysanthemic acid esters and their use in pest control

ABSTRACT

An ester compound represented by formula (1): wherein R 3  represents hydrogen or methyl, R 4  represents hydrogen or C1-C4 alkyl, and R 5  represents hydrogen or C1-C4 alkyl; has an excellent pest control effect and is therefore useful as an active ingredient of a pest control agent.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Section 371 of International Application No.PCT/JP2011/057504, filed Mar. 18, 2011, which was published in theEnglish language on Oct. 6, 2011, under International Publication No. WO2011/122509 A1, and the disclosure of which is incorporated herein byreference.

TECHNICAL FIELD

The present invention relates to an ester compound and use thereof.

BACKGROUND ART

Heretofore, various compounds have been synthesized so as to controlpests. For example, a certain ester compound is described inJP-A-57-158765.

DISCLOSURE OF INVENTION

An object of the present invention is to provide a novel compound havingan excellent pest control effect.

The present inventors have intensively studied and found that an estercompound represented by formula (1) shown below has an excellent pestcontrol effect, and led to the present invention.

That is, the present invention is directed to the following invention:

[1] An ester compound represented by formula (1):

wherein R³ represents hydrogen or methyl, R⁴ represents hydrogen orC1-C4 alkyl, and R⁵ represents hydrogen or C1-C4 alkyl(hereinafter referred to as the compound of the present invention);[2] The ester compound according to [1], wherein a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration in formula (1);[3] The ester compound according to [1], wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration in formula (1);[4] The ester compound according to [1], wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration in formula(1);[5] The ester compound according to [1], wherein a relativeconfiguration of the substituent of the 1′-position existing on thesubstituent at the 3-position of the cyclopropane ring isZ-configuration in formula (1);[6] The ester compound according to [1], wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration in formula (1);[7] The ester compound according to [1], wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration in formula (1);[8] The ester compound according to any one of [1] to [7], wherein R³ ishydrogen in formula (1);[9] The ester compound according to any one of [1] to [7], wherein R⁴ ishydrogen or methyl in formula (1);[10] The ester compound according to any one of [1] to [7], wherein R⁴is hydrogen in formula (1);[11] The ester compound according to any one of [1] to [7], wherein R⁴is methyl in formula (1);[12] The ester compound according to any one of [1] to [7], wherein R⁵is hydrogen in formula (1);[13] The ester compound according to any one of [1] to [7], wherein R³is hydrogen and R⁴ is hydrogen or methyl in formula (1);[14] The ester compound according to any one of [1] to [7], wherein R³is hydrogen and R⁴ is hydrogen in formula (1);[15] The ester compound according to any one of [1] to [7], wherein R³is hydrogen and R⁴ is methyl in formula (1);[16] The ester compound according to any one of [1] to [7], wherein R³is hydrogen and R⁵ is hydrogen in formula (1);[17] The ester compound according to any one of [1] to [7], wherein R⁴is hydrogen or methyl, and R⁵ is hydrogen in formula (1);[18] The ester compound according to any one of [1] to [7], wherein R⁴is hydrogen and R⁵ is hydrogen in formula (1);[19] The ester compound according to any one of [1] to [7], wherein R⁴is methyl and R⁵ is hydrogen in formula (1);[20] The ester compound according to any one of [1] to [7], wherein R³is hydrogen, R⁴ is hydrogen or methyl, and R⁵ is hydrogen in formula(1);[21] The ester compound according to any one of [1] to [7], wherein R³is hydrogen, R⁴ is hydrogen, and R⁵ is hydrogen in formula (1);[22] The ester compound according to any one of [1] to [7], wherein R³is hydrogen, R⁴ is methyl; and R⁵ is hydrogen in formula (1);[23] A pest control agent comprising the ester compound according to anyone of [1] to [22] and an inert barrier;[24] A method of controlling pests, which comprises a step of applyingan effective amount of the ester compound according to any one of [1] to[22] to pests or a place where pests habitat;[25] A method of controlling pests, which comprises the step of applyingan effective amount of the ester compound according to any one of [1] to[22] to cockroaches or a place where cockroaches inhabits;[26] The method of controlling pests according to [25], wherein thecockroach is American cockroach (Periplaneta Americana);[27] The method of controlling pests according to [25], wherein thecockroach is German cockroach (Blattella germanica);[28] A method of controlling pests, which comprises a step of sprayingan effective amount of the ester compound according to any one of [1] to[22] to cockroaches or a place where cockroaches inhabit;[29] The method of controlling pests according to [28], wherein thecockroach is American cockroach (Periplaneta Americana);[30] The method of controlling pests according to [28], wherein thecockroach is German cockroach (Blattella germanica).

The compound of the present invention has an excellent pest controleffect and is therefore useful as an active ingredient of a pest controlagent.

In the compound of the present invention, there are isomers derived fromtwo asymmetric carbon atoms at the 1-position and the 3-position on thecyclopropane ring, and isomers derived from the double bond present inthe substituent at the 3-position of the cyclopropane ring. Each isomerhaving pest control activity or a mixture of those isomers in anarbitrary ratio which has pest control activity are included in thepresent invention.

Examples of the C1-C4 alkyl represented by R⁴ include methyl, ethyl,propyl, butyl and isopropyl, and the C1-C4 alkyl represented by R⁵include methyl, ethyl, propyl, butyl and isopropyl.

Examples of the compound of the present invention include the followingcompounds.

An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration.

An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration.

An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent of the 1′-position existing on thesubstituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R³ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, and R³ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and R³ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and R³ ishydrogen.An ester compound represented by formula (1) in which R³ is hydrogen anda relative configuration of the substituent of the 1′-position existingon the substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R³ is hydrogen andan absolute configuration of the 1-position of the cyclopropane ring isan R configuration and a relative configuration of the substituent ofthe 1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, anabsolute configuration of the 1-position of the cyclopropane ring is anR configuration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, and R⁴ is hydrogen or methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and R⁴ is hydrogen or methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration; and R⁴ ishydrogen or methyl.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl, and an absolute configuration of the 1-position of thecyclopropane ring is an R configuration and a relative configuration ofthe substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl, an absolute configuration of the 1-position of the cyclopropanering is an R configuration, a relative configuration of the substituentat the 1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, and R⁴ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and R⁴ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and R⁴ ishydrogen.An ester compound represented by formula (1) in which R⁴ is hydrogen anda relative configuration of the substituent of the 1′-position existingon the substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen andan absolute configuration of the 1-position of the cyclopropane ring isan R configuration and a relative configuration of the substituent ofthe 1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen, anabsolute configuration of the 1-position of the cyclopropane ring is anR configuration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁴ is methyl.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, and R⁴ is methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and R⁴ is methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and R⁴ ismethyl.An ester compound represented by formula (1) in which R⁴ is methyl and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁴ is methyl andan absolute configuration of the 1-position of the cyclopropane ring isan R configuration and a relative configuration of the substituent ofthe 1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is methyl, anabsolute configuration of the 1-position of the cyclopropane ring is anR configuration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and R⁵ ishydrogen.An ester compound represented by formula (1) in which R⁵ is hydrogen anda relative configuration of the substituent of the 1′-position existingon the substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁵ is hydrogen andan absolute configuration of the 1-position of the cyclopropane ring isan R configuration and a relative configuration of the substituent ofthe 1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁵ is hydrogen, anabsolute configuration of the 1-position of the cyclopropane ring is anR configuration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R³ is hydrogen andR⁴ is hydrogen or methyl.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R³ is hydrogen and R⁴ is hydrogen or methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an RConfiguration, and R³ is hydrogen and R⁴ is hydrogen or methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R³ ishydrogen and R⁴ is hydrogen or methyl.An ester compound represented by formula (1) in which R³ is hydrogen andR⁴ is hydrogen or methyl, and a relative configuration of thesubstituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen or methyl, and an absolute configuration of the 1-positionof the cyclopropane ring is an R configuration and a relativeconfiguration of the substituent of the 1′-position existing on thesubstituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen or methyl, an absolute configuration of the 1-position ofthe cyclopropane ring is an R configuration, a relative configuration ofthe substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen andR⁴ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R³ is hydrogen and R⁴ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and R³ is hydrogen and R⁴ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R³ ishydrogen and R⁴ is hydrogen.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen, and an absolute configuration of the 1-position of thecyclopropane ring is an R configuration and a relative configuration ofthe substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen, an absolute configuration of the 1-position of thecyclopropane ring is an R configuration, a relative configuration of thesubstituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-1-5 position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen andR⁴ is methyl.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R³ is hydrogen and R⁴ is methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R³ is hydrogen and R⁴ is methyl.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R³ ishydrogen and R⁴ is methyl.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is methyl and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is methyl, and an absolute configuration of the 1-position of thecyclopropane ring is an R configuration and a relative configuration ofthe substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is methyl, an absolute configuration of the 1-position of thecyclopropane ring is an R configuration, a relative configuration of thesubstituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen andR⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R³ is hydrogen and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R³ is hydrogen and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R³ ishydrogen and R⁵ is hydrogen.An ester compound represented by formula (1) in which R³ is hydrogen, R⁵is hydrogen and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁵is hydrogen, and an absolute configuration of the 1-position of thecyclopropane ring is an R configuration and a relative configuration ofthe substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁵is hydrogen, an absolute configuration of the 1-position of thecyclopropane ring is an R configuration, a relative configuration of thesubstituent at the 1-positioned of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R⁴ is hydrogen or methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R⁴ is hydrogen or methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R⁴ ishydrogen or methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl, R⁵ is hydrogen, and a relative configuration of the substituentof the 1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl, R⁵ is hydrogen, and an absolute configuration of the 1-positionof the cyclopropane ring is an R configuration and a relativeconfiguration of the substituent of the 1′-position existing on thesubstituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen ormethyl, R⁵ is hydrogen, an absolute configuration of the 1-position ofthe cyclopropane ring is an R configuration, a relative configuration ofthe substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen andR⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R⁴ is hydrogen and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R⁴ is hydrogen and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R⁴ ishydrogen and R⁵ is hydrogen. An ester compound represented by formula(1) in which R⁴ is hydrogen, R⁵ is hydrogen, and a relativeconfiguration of the substituent of the 1′-position existing on thesubstituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen, R⁵is hydrogen and an absolute configuration of the 1-position of thecyclopropane ring is an R configuration and a relative configuration ofthe substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is hydrogen, R⁵is hydrogen, an absolute configuration of the 1-position of thecyclopropane ring is an R configuration, a relative configuration of thesubstituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is methyl andR⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R⁴ is methyl and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R⁴ is methyl and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R⁴ ismethyl and R⁵ is hydrogen.An ester compound represented by formula (1) in which R⁴ is methyl, R⁵is hydrogen, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is methyl, R⁵is hydrogen and an absolute configuration of the 1-position of thecyclopropane ring is an R configuration and a relative configuration ofthe substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R⁴ is methyl, R⁵is hydrogen, an absolute configuration of the 1-position of thecyclopropane ring is an R configuration, a relative configuration of thesubstituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen or methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R³ is hydrogen, R⁴ is hydrogen or methyl, and R⁵ ishydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R³ is hydrogen, R⁴ is hydrogen or methyl, and R⁵ ishydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R³ ishydrogen, R⁴ is hydrogen or methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen or methyl, R⁵ is hydrogen, and a relative configuration ofthe substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen or methyl, R⁵ is hydrogen, and an absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration and arelative configuration of the substituent of the 1′-position existing onthe substituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented, by formula (1) in which R³ is hydrogen,R⁴ is hydrogen or methyl, R⁵ is hydrogen, an absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative, configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, and a relative configurationof the substituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen, and R⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R³ is hydrogen, R⁴ is hydrogen, and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R³ is hydrogen, R⁴ is hydrogen, and R⁵ is hydrogen.An ester compound represented by formula (1) in'which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R³ ishydrogen, R⁴ is hydrogen, and R⁵ is hydrogen.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen, R⁵ is hydrogen, and a relative configuration of thesubstituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen, R⁵ is hydrogen, and an absolute configuration of the1-position of the cyclopropane ring is an R configuration and a relativeconfiguration of the substituent of the 1′-position existing on thesubstituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is hydrogen, R⁵ is hydrogen, an absolute configuration of the 1-positionof the cyclopropane ring is an R configuration, a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, R³ is hydrogen, R⁴ is methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, R³ is hydrogen, R⁴ is methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration, R³ ishydrogen, R⁴ is methyl, and R⁵ is hydrogen.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is methyl, R⁵ is hydrogen, and a relative configuration of thesubstituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is methyl, R⁵ is hydrogen, and an absolute configuration of the1-position of the cyclopropane ring is an R configuration and a relativeconfiguration of the substituent of the 1′-position existing on thesubstituent at the 3-position of the cyclopropane ring isZ-configuration.An ester compound represented by formula (1) in which R³ is hydrogen, R⁴is methyl, R⁵ is hydrogen, an absolute configuration of the 1-positionof the cyclopropane ring is an R configuration, a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration.

The process for producing the compound of the present invention will bedescribed below.

The compound of the present invention can be produced, for example, bythe production process described below.

A process of reacting an alcohol compound represented by the formula(2):

with a carboxylic acid compound represented by the formula (3):

(wherein R³, R⁴ and R⁵ have the same meanings as defined above),or a reactive derivative thereof.

Examples of the reactive derivative include an acid halide of thecarboxylic acid compound represented by the formula (3), an acidanhydride of the carboxylic acid compound, and methyl and ethyl estersof the carboxylic acid compound. Examples of the acid halide include anacid chloride compound.

The reaction is usually, carried out in the presence a condensing agentor a base in a solvent.

Examples of the condensing agent include dicyclohexylcarbodiimide and1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride.

Examples of the base include organic bases such as triethylamine,pyridine, N,N-diethylaniline, 4-dimethylaminopyridine anddiisopropylethylamine.

Examples of the solvent include hydrocarbons such as benzene, tolueneand hexane; ethers such as diethylether and tetrahydrofuran; halogenatedhydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane andchlorobenzene; and a mixed solvent thereof.

The reaction time is usually within a range from 5 minutes to 72 hours.

The reaction temperature is usually within a range from −20° C. to 100°C. (from −20° C. to a boiling point of the solvent in a case a boilingpoint of the solvent used is lower than 100° C.), and preferably −5° C.to 100° C. (from −5° C. to a boiling point of the solvent in a case aboiling point of the solvent used is lower than 100° C.).

In the reaction, a use molar ratio of the alcohol compound representedby the formula (2) to the carboxylic acid compound represented by theformula (3) or the reactive derivative thereof can be optionally set,but is preferably an equimolar or near equimolar ratio.

The condensing agent or base can be usually used in any amount within arange from 0.25 mol to an excess amount, and preferably from 0.5 mol to2 mol, based on 1 mol of the alcohol compound represented by the formula(2). These condensing agents or bases are appropriately selectedaccording to the kind of the carboxylic acid compound represented by theformula (3) or the reactive derivative thereof.

After completion of the reaction, the reaction mixture is usuallysubjected to a post-treatment operation of filtering the reactionmixture and concentrating the filtrate, or pouring water into thereaction mixture, followed by extraction with an organic solvent andfurther concentration, and thus the compound of the present inventioncan be obtained. The obtained compound of the present invention can bepurified by operations such as chromatography and distillation.

The alcohol compound represented by the formula (2) is a compounddescribed in JP-A-05-255271.

The intermediate of the present invention can be produced, for example,by the following process.

Among the carboxylic acid compound represented by the formula (3), thecarboxylic acid compound represented by the formula (3-1) in whichrelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is trans configuration can be produced, for example,by the following process.

That is, a carboxylic acid compound represented by the formula (3-1):

(wherein R³, R⁴ and R⁵ have the same meanings as defined above), can beproduced by reacting a caronaldehyde ester derivative represented by theformula (4-1):

(wherein R represents a C1-C4 alkyl group), with a nitrile compoundrepresented by the formula (5):

(wherein R³, R⁴ and R⁵ have the same meanings as defined above), in thepresence of a base to obtain the compound represented by the formula(6-1):

(wherein R, R³, R⁴ and R⁵ have the same meanings as defined), andfurther hydrolyzing the obtained compound in the presence of a base.

The compound represented by the formula (6-1) can be usually produced byreacting in a polar solvent at a temperature within a range from 0° C.to 80° C., and preferably from 0° C. to 30° C., using the nitrilecompound represented by the formula (5) in the amount of 1.0 to 1.5 moland a base in the mount of 1 to 10 mol, based on 1 mol of thecaronaldehyde ester derivative represented by the formula (4-1).Examples of the base include carbonates such as potassium carbonate andsodium carbonate; and alkali metal compounds such as sodium hydride.Examples of the polar solvent include acid amides such asN,N-dimethylformamide; and sulfoxide such as dimethyl sulfoxide.

After completion of the reaction, the reaction mixture is subjected to apost-treatment operation of adding water, followed by extraction with anorganic solvent and further drying and concentration of the organiclayer, and thus the compound represented by the formula (6-1) can beobtained.

In the step of hydrolyzing the compound represented by the formula(6-1), the carboxylic acid compound represented by the formula (3-1) canbe usually produced by reacting in a solvent at a temperature of 0° C.to 80° C., and preferably 0° C. to 30° C., using a base in the amount of1 to 10 mol based on mol of the compound represented by the formula(6-1). Examples of the base include carbonic acid alkali metal saltssuch as potassium carbonate and sodium carbonate; and alkali metalcompounds such as sodium hydride. Examples of the solvent include etherssuch as tetrahydrofuran; alcohols such as methanol; water; and a mixturethereof.

After completion of the reaction, the reaction solution is subjected toa post-treatment operation of acidifying, followed by extraction with anorganic solvent and further drying and concentration of the organiclayer, and thus the carboxylic acid compound represented by the formula(3-1) can be obtained.

Among the carboxylic acid compound represented by the formula (3), acarboxylic acid compound represented by the formula (3-2) in whichrelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is cis configuration can be produced, for example, bythe following process.

That is, the carboxylic acid compound represented by the formula (3-2):

(wherein R³, R⁴ and R⁵ have the same meanings as defined above), can beproduced by reacting a caronaldehyde ester derivative represented by theformula (4-2):

with the nitrile derivative represented by the formula (5):

(wherein R³, R⁴ and R⁵ have the same meanings as defined above), in thepresence of a base to obtain a compound represented by the formula(6-2):

(wherein R³, R⁹ and R⁵ have the same meanings as defined above), andheating the obtained compound in the presence of an acid catalyst.

The compound represented by the formula (6-2) can be usually produced byreacting in a polar solvent at a temperature of 0° C. to 80° C., andpreferably 0° C. to 30° C., using the nitrile compound represented bythe formula (5) in the amount of 1.0 to 1.5 mol and a base in the amountof 1 to 10 mol, based on 1 mol of the caronaldehyde ester derivativerepresented by the formula (4-2). Examples of the base includecarbonates such as potassium carbonate and sodium carbonate; and alkalimetal compounds such as sodium hydride. Examples of the polar solventinclude acid amides such as N,N-dimethylformamide; and sulfoxides suchas dimethyl sulfoxide.

After completion of the reaction, the reaction mixture is subjected to apost-treatment operation of adding water, followed by extraction with anorganic solvent and further drying and concentration of the organiclayer, and thus the compound represented by the formula (6-2) can beobtained.

In the step of producing the compound represented by the formula (3-2)from the compound represented by the formula (6-2), the reaction iscarried out at a reaction temperature of usually 50° C. to 150° C. (50°C. to a boiling point of the solvent in a case a boiling point of thesolvent is lower than 150° C.), using an acid catalyst in the amount of0.005 to 0.05 mol based on 1 mol of the compound represented by theformula (6-2), and thus the carboxylic acid compound represented by theformula (3-2) can be produced. Examples of the acid catalyst includep-toluenesulfonic acid and the like. Examples of the solvent includeethers such as tetrahydrofuran; hydrocarbons such as toluene; and amixture thereof.

After completion of the reaction, the carboxylic acid compoundrepresented by the formula (3-2) can be obtained by subjecting to apost-treatment operation of drying and concentrating of the organiclayer.

The caronaldehyde ester derivative represented by the formula (4-1) iscompound described in Tetrahedron 45, 3039-3052 (1989).

The caronaldehyde ester derivative represented by the formula (4-2) is acompound described in Journal of American Chemical Society, 1982, 104,4282-4283.

The nitrile compound represented by the formula (5) can be synthesizedaccording to a known method such as described in Journal of AmericanChemical Society, 2008, 130, 3734.

Examples of pests on which the compound of the present invention has acontrol effect include harmful arthropod pests such as harmful insectsand harmful acarines, and more specifically, the following pests.

Hemiptera: planthoppers such as Laodelphax striatellus, Nilaparvatalugens, and Sogatella furcifera, leafhoppers such as Nephotettixcincticeps, and Nephotettix virescens, aphids such as Aphis gossypii,and Myzus persicae, plant bugs such as Nezara antennata, Riptortusclavetus, Eysarcoris lewisi, Eysarcoris parvus, Plautia stali, andHalyomorpha mista, white flies such as Trialeurodes vaporariorum,Bemisia tabaci, and Bemisia argentifolii, scales such as Aonidiellaaurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens,and Icerya purchasi, lace bugs, bed bugs such as Cimex lectularius,jumping plantlice and so on;

Lepidoptera: Pyralidae such as Chilo suppressalis, Cnaphalocrocismedinalis, Notarcha derogata, and Plodia interpunctella, Spodopteralitura, Pseudaletia separata, Noctuidae such as Trichoplusia spp.,Heliothis spp., and Earias spp., Pieridae such as Pieris rapae,Tortricidae such as Adoxopheys spp., Grapholita molesta, Adoxophyesorana fasciata, and Cydia pomonella, Carposinidae such as Carposinaniponensis, Lyonetiidae such as Lyonetia spp., Lymantriidae such asLymantria spp., Lymantriidae such as Euproctis spp., Yponameutidae suchas Plutella xylostella, Gelechiidae such as Pectinophora gossypiella,Arctiidae such as Hyphantria cunea, Tineidae such as Tinea translucens,and Tineola bisselliella, and so on;

Diptera: Culex spp. such as Culex pipiens pallens, Culextritaeniorhynchus, and Culex quinquefasciatus, Aedes spp. such as Aedesaegypti, and Aedes albopictus, Anopheles spp. such as Anophelessinensis, and Anopheles gambiae, Chironomidae, Muscidae such as Muscadomestica, and Muscina stabulans, Calliphoridae, Sarcophagidae, littlehousefly, Anthomyiidae such as Delia platura, and Delia antiqua,Tephritidae, Drosophilidae, Phoridae such as Megaselia spiracularis,Clogmia albipunctata, Psychodidae, Simuliidae, Tabanidae, Stomoxyidae,Agromyzidae, and so on;

Coleoptera: Diabrotica spp. such as Diabrotica virgifera virgifera, andDiabrotica undecimpunctata howardi, Scarabaeidae such as Anomala cuprea,and Anomala rufocuprea, Curculionidae such as Sitophilus zeamais,Lissorhoptrus oryzophilus, and Callosobruchuys chienensis, Tenebrionidaesuch as Tenebrio molitor, and Tribolium castaneum, Chrysomelidae such asOulema oryzae, Aulacophora femoralis, Phyllotreta striolata, andLeptinotarsa decemlineata, Dermestidae such as Dermestes maculates,Anobiidae, Epilachna spp. such as Epilachna vigintioctopunctata,Lyctidae, Bostrychidae, Ptinidae, Cerambycidae, Paederus fuscipes, andso on;

Blattodea: Blattella germanica, Periplaneta fuliginosa, Periplanetaamericana, Periplaneta brunnea, Blatta orientalis, and so on;

Thysanoptera: Thrips palmi, Thrips tabaci, Frankliniella occidentalis,Frankliniella intonsa, and so on;

Hymenoptera: Formicidae such as Monomorium pharaosis, Formica fuscajaponica, Ochetellus glaber, Pristomyrmex pungens, Pheidole noda, andLinepithema humile, long-legged wasps such as Polistes chinensisantennalis, Polistes jadwigae, and Polistes rothneyi, Vespidae such asVespa mandarinia japonica, Vespa simillima, Vespa analis insularis,Vespa crabro flavofasciata, and Vespa ducalis, Bethylidae, Xylocopa,Pompilidae, Sphecoidae, mason wasp, and so on;

Orthoptera: mole crickets, grasshoppers, etc.;

Shiphonaptera: Ctenocephalides felis, Ctenocephalides canis, Pulexirritans, Xenopsylla cheopis, and so on;

Anoplura: Pediculus humanus corporis, Phthirus pubis, Haematopinuseurysternus, Dalmalinia ovis, and so on;

Isoptera: Reticulitermes spp. such as Reticulitermes speratus,Coptotermes formosanus, Reticulitermes flavipes, Reticulitermeshesperus, Reticulitermes virginicus, Reticulitermes tibialis, andHeterotermes aureus, Incisitermes spp. such as Incisitermes minor, andZootermopsis spp. such as Zootermopsis nevadensis, and so on;

Acarina: Tetranychidae such as Tetranychus urticae, Tetranychuskanzawai, Panonychus citri, Panonychus ulmi, and Oligonychus spp.,Eriophyidae such as Aculops pelekassi, and Aculus schlechtendali,Tarsonemidae such as Polyphagotarsonemus latus, Tenuipalpidae,Tuckerellidae, Ixodidae such as Haemaphysalis longicornis, Haemaphysalisflava, Dermacentor variabilis, Ixodes ovatus, Ixodes persulcatus),Ixodes scapularis, Boophilus microplus, Amblyomma americanum, andRhipicephalus sanguineus, Acaridae such as Tyrophagus putrescentiae,Dermanyssidae such as Dermatophagoides farinae, Dermatophagoidesptrenyssnus, Cheyletidae such as Cheyletus eruditus, Cheyletusmalaccensis, and Cheyletus moorei, chicken mite such as Ornithonyssusbacoti, Ornithonyssus sylvairum, and Dermanyssus gallinae, Trombiculidaesuch as Leptotrombidium akamushi, and so on;

Araneae: Japanese foliage spider (Chiracanthium japonicum), redbackspider (Latrodectus hasseltii), Nephila clavata (Tetragnathidae),Cyclosa octotuberculata, St. Andrew's cross spider (Argiope amoena),Wasp spider (Argiope bruennichii), orb-weaving spider (Araneusventricosus), grass spider (Agelena silvatica), wolf spider (Pardosaastrigera), dock spider (Dolomedes sulfurous), Carrhotus xanthogramma,common house spider (Achaearanea tepidariorum), Coelotes insidiosus,jumping spider (Salticidae), huntsman spider (Heteropoda venatoria),etc.;

Chilopoda: centipedes such as house centipede (Thereuonema hilgendorfi),Scolopendra subspinipes, Scolopendra subspinipes japonica,Scolopocryptops rubiginosus, Bothropolys asperatus, etc.;

Diplopoda: millipedes such as garden millipede (Oxidus gracilis), gardenmillipede (Nedyopus tambanus), train millipede (Parafontaria laminate),train millipede (Parafontaria laminata armigera), Parafontariaacutidens, Epanerchodus orientalis, etc.;

Isopoda: sow bugs such as Porcellionides pruinosus (Brandt), Porcellioscaber Latreille, pill bugs such as common pill bug (Armadillidiumvulgare), sea louses such as wharf roach (Ligia exotica), etc.;

Gastropoda: tree slug (Limax marginatus), yellow slug (Limax flavus),etc.

The pest control agent of the present invention contains the compound ofthe present invention and an inert carrier. The pest control agent ofthe present invention is usually formed into formulations describedbelow. Examples of the formulation include an oil solution, anemulsifiable concentrate, a wettable powder, a flowable formulation(e.g., an aqueous suspension, or an aqueous emulsion), a microcapsule, adust, a granule, a tablet, an aerosol, a carbon dioxide formulation, aheat transpiration formulation (e.g., an insecticidal coil, an electricinsecticidal mat, or a liquid absorbing core-type heat transpirationpesticide), a piezo insecticidal formulation, a heat fumigant (e.g., aself combustion-type fumigant, a chemical reaction-type fumigant, or aporous ceramic plate fumigant), an unheated transpiration formulation(e.g., a resin transpiration formulation, a paper transpirationformulation, an unwoven fabric transpiration formulation, a knit fabrictranspiration formulation, or a sublimating tablet), an aerosolformulation (e.g., a fogging formulation), a direct contact formulation(e.g., a sheet-shaped contact formulation, a tape-shaped contactformulation, or a net-shaped contact formulation), an ULV formulationand a poison bait

Examples of the method for formulation include the following methods.

(1) A method comprising mixing the compound of the present inventionwith a solid carrier, a liquid carrier, a gaseous carrier or a poisonbait, followed by addition of a surfactant and other auxiliary agentsfor formulation, and if necessary, further processing.(2.) A method comprising impregnation of a base material containing noactive ingredient with the compound of the present invention.(3) A method comprising mixing the compound of the present invention anda base material, followed by subjecting the mixture to mold processing.

These formulations usually contain 0.001 to 98% by weight of thecompound of the present invention, depending on formulation forms.

Examples of the solid carrier used in the formulation include finepowders or granules of clays (e.g., kaolin clay, diatomaceous earth,bentonite, Fubasami clay, or acid white clay), synthetic hydratedsilicon oxide, talc, ceramics, other inorganic minerals (e.g., sericite,quartz, sulfur, active carbon, calcium carbonate, or hydrated silica)and fine powder and granulated substances such as chemical fertilizers(e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammoniumchloride, or urea); substances that are solid at room temperature (e.g.,2,4,6-triisopropyl-1,3,5-trioxane, naphthalene, p-dichlorobenzene, orcamphor, adamantine); as well as felt, fiber, fabric, knit, sheet,paper, thread, foam, porous material and multi-filament comprising oneor more substances selected from the group consisting of wool, silk,cotton, hemp, pulp, synthetic resins (e.g., polyethylene resins such aslow density polyethylene, straight chain low density polyethylene andhigh density polyethylene; ethylene-vinyl ester copolymers such as anethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers suchas an ethylene-methyl methacrylate copolymer and an ethylene-ethylmethacrylate copolymer; ethylene-acrylate copolymers such as anethylene-methyl acrylate copolymer and an ethylene-ethyl acrylatecopolymer; ethylene-vinylcarboxylic acid copolymers such as anethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers;polypropylene resins such as a propylene homopolymer and apropylene-ethylene copolymer; poly-4-methylpentene-1, polybutene-1,polybutadiene, polystyrene; acrylonitrile-styrene resin;acrylonitrile-butadiene-styrene resins; styrene elastomers such as astyrene-conjugated diene block copolymer and a hydrogenatedstyrene-conjugated diene block copolymer; fluorine resins; acrylicresins such as methyl polymethacrylate; polyamide resins such as nylon 6and nylon 66; polyester resins such as polyethylene terephthalate,polyethylene naphthalate, polybutylene terephthalate andpolycyclohexylene dimethylene terephthalate; or porous resins such aspolycarbonate, polyacetal, polyacryl sulfone, polyarylate,hydroxybenzoic acid polyester, polyetherimide, polyester carbonate,polyphenylene ether resins, polyvinyl chloride, polyvinylidene chloride,polyurethane, foamed polyurethane, foamed polypropylene and foamedethylene), glass, metal and ceramics.

Examples of the liquid carrier include aromatic or aliphatichydrocarbons (e.g., xylene, toluene, alkylnaphthalene,phenylxylylethane, kerosene, light oil, hexane, or cyclohexane),halogenated hydrocarbons (e.g., chlorobenzene, dichloromethane,dichloroethane, or trichloroethane), alcohols (e.g., methanol, ethanol,isopropyl alcohol, butanol, hexanol, benzyl alcohol, or ethyleneglycol), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,propylene glycol monomethyl ether, tetrahydrofuran, or dioxane), esters(e.g., ethyl acetate, or butyl acetate), ketones (e.g., acetone, methylethyl ketone, methyl isobutyl ketone, or cyclohexanone), nitriles (e.g.,acetonitrile, or isobutyronitrile), sulfoxides (e.g., dimethylsulfoxide), acid amides (e.g., N,N-dimethylformamide,N,N-dimethylacetamide, or N-methyl-pyrrolidone), alkylidene carbonate(e.g., propylene carbonate), vegetable oils (e.g., soybean oil, orcottonseed oil), plant essential oils (e.g., orange oil, hyssop oil, orlemon oil), and water.

Examples of the gaseous carrier include butane gas, chlorofluorocarbon,liquefied petroleum gas (LPG), dimethyl ether and carbon dioxide.

Examples of the surfactant include alkyl sulfate, alkyl sulfonate,alkylaryl sulfonate, alkylaryl ethers, polyoxyethylenated alkylarylethers, polyethylene glycol ethers, polyhydric alcohol esters and sugaralcohol derivatives.

Examples of the other auxiliary agents for formulation include a binder,a dispersant and a stabilizer.

Specifically, there are, for example, casein, gelatin, polysaccharides(e.g., starch, gum arabic, cellulose derivatives, or alginic acid),lignin derivatives, bentonite, saccharides, synthetic water-solublepolymers (e.g., polyvinyl alcohol, or polyvinyl pyrrolidone),polyacrylic acid, BHT (2,6-di-tert-butyl-4-methylphenol) and BHA (amixture of 2-tert-butyl-4-methoxyphenol and3-tert-butyl-4-methoxyphenol).

Examples of a base material for the insecticidal coil include a mixtureof vegetable powder such as wood flour and lees powder, and a bindersuch as incense material powder, starch and gluten.

Examples of a base material for the electric insecticidal mat include aplate obtained by hardening cotton linter and a plate obtained byhardening fibrils of a mixture of cotton linter and pulp.

Examples of a base material for the self combustion-type fumigantinclude combustible exothermic agents such as nitrate, nitrite,guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose andwood flour, thermal decomposition stimulants such as alkali metal salt,alkaline earth metal salt, dichromate and chromate, oxygen carriers suchas potassium nitrate, combustion-supporting agents such as melamine andflour starch, extenders such as diatomaceous earth, and binders such assynthetic glue.

Examples of a base material for the chemical reaction-type fumigantinclude exothermic agents such as alkali metal sulfide, polysulfide,hydrosulfide and calcium oxide, catalytic agents such as a carbonaceousmaterial, iron carbide and active white clay, organic foaming agentssuch as azodicarbonamide, benzenesulfonylhydrazide,dinitropentamethylenetetramine, polystyrene and polyurethane, andfillers such as strips of natural fiber and synthetic fiber.

Examples of a resin used as a base material of the resin transpirationformulation include polyethylene resins such as low densitypolyethylene, straight chain low density polyethylene and high densitypolyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinylacetate copolymer; ethylene-methacrylate copolymers such as anethylene-methyl methacrylate copolymer and an ethylene-ethylmethacrylate copolymer; ethylene-acrylate copolymers such as anethylene-methyl acrylate copolymer and an ethylene-ethyl acrylatecopolymer; ethylene-vinylcarboxylic acid copolymers such as anethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers;polypropylene resins such as a propylene copolymer and apropylene-ethylene copolymer; poly-4-methylpentene-1, polybutene-1,polybutadiene, polystyrene, acrylonitrile-styrene resins;acrylonitrile-butadiene-styrene resins; styrene elastomers such as astyrene-conjugated diene block copolymer and a hydrogenatedstyrene-conjugated diene block copolymer; fluorine resins; acrylicresins such as methyl polymethacrylate; polyamide resins such as nylon 6and nylon 66; polyester resins such as polyethylene terephthalate,polyethylene naphthalate, polybutylene butalate and polycyclohexylenedimethylene terephthalate; polycarbonate, polyacetal, polyacryl sulfone,polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyestercarbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidenechloride and polyurethane. These base materials may be used alone or asa combination of two or more kinds. If necessary, a plasticizer such asphthalate esters (e.g., dimethyl phthalate, dioctyl phthalate, etc.),adipic acid esters and stearic acid may be added to these basematerials. The resin transpiration formulation can be prepared by mixingthe compound of the present invention with the base material, kneadingthe mixture, followed by molding it by injection molding, extrusionmolding or pressure molding. The resultant resin formulation can besubjected to further molding or cutting procedure, if necessary, to beprocessed into shapes such as a plate, film, tape, net or string shape.These resin formulations can be processed into animal collars, animalear tags, sheet products, trap strings, gardening supports and otherproducts.

Examples of a base material for the poison bait include bait ingredientssuch as grain powder, vegetable oil, saccharide and crystallinecellulose, antioxidants such as dibutylhydroxytoluene andnordihydroguaiaretic acid, preservatives such as dehydroacetic acid,accidental ingestion inhibitors for children and pets such as a chilipowder; insect attraction fragrances such as cheese flavor, onion flavorand peanut oil.

The pest control method of the present invention usually conducted byapplying an effective amount of the compound of the present invention toa pest or a habitat thereof (e.g. plant bodies, soil, the interior of ahouse, animal bodies, the interior of a car, or outdoor open space) in aform of a pest control agent of the present invention.

A method for applying the pest control agent of the present inventionincludes the following methods, and appropriately selected depending onthe form of the pest control agent of the present invention, theapplication area and so on.

(1) A method comprising applying a pest control agent of the presentinvention as it is to a pest of a habitat of the pest.

(2) A method comprising diluting a pest control agent of the presentinvention with a solvent such as water, and then spraying the dilutionto a pest or a habitat of the pest. In this method, the pest controlagent of the present invention is usually formulated into anemulsifiable concentrate, a wettable powder, a flowable formulation, amicrocapsule or the like. The formulation is usually diluted so that theconcentration of the compound of the present invention can be 0.1 to10,000 ppm.(3) A method comprising heating a pest control agent of the presentinvention at a habitat of a pest, thereby allowing an active ingredientto volatilize and diffuse from the pest control agent.In this case, any of the amount and concentration of application of thecompound of the present invention can be appropriately determineddepending on the form, application period, application area, applicationmethod, kind of a pest, damage to be incurred and so on.

When the compound of the present invention is used for prevention ofepidemics, the amount to be applied is usually from 0.0001 to 1,000mg/m³ of the compound of the present invention in the case of applyingto a space, and from 0.0001 to 1,000 mg/m² of the compound of thepresent invention in the case of applying to a plane. An insecticidalcoil or an electric insecticidal mat is applied by heating to volatilizeand diffuse an active ingredient, depending on the form of theformulation. A resin transpiration formulation, a paper transpirationformulation, an unwoven fabric transpiration formulation, a knit fabrictranspiration formulation or a sublimating tablet are allowed to standas it is in a space to be applied, and placed under air blowing.

When the pest control agent of the present invention is applied to aspace for the purpose of prevention of epidemics, examples of the spaceinclude a closet, a Japanese cabinet, a Japanese chest, a cupboard, atoilet, a bathroom, a shed, a living room, a dining room, a garage, theinterior of a car and so on. The pest control agent can be also appliedto outdoor open space.

When the pest control agent of the present invention is used forcontrolling external parasites of livestock such as cows, horses, pigs,sheep, goats and chickens and small animals such as dogs, cats, rats andmice, the pest control agent of the present invention can be applied tothe animals by a known method in the veterinary field. Specifically,when systemic control is intended, the pest control agent of the presentinvention is administered to the animals as a tablet, a mixture withfeed or a suppository, or by injection (including intramuscular,subcutaneous, intravenous and intraperitoneal injections). On the otherhand, when non-systemic control is intended, the pest control agent ofthe present invention is applied to the animals by means of spraying ofthe oil solution or aqueous solution, pour-on or spot-on treatment, orwashing of the animal with a shampoo formulation, or by putting a collaror ear tag made of the resin transpiration formulation to the animal. Inthe case of administering to an animal body, the dosage of the compoundof the present invention is usually in the range from 0.1 to 1,000 mgper 1 kg of an animal body weight.

When the pest control agent of the present invention is used forcontrolling a pest in the agricultural field, the amount can widely varydepending on the application period, application area, applicationmethod and other factors, and is usually in the range from 1 to 10,000 gin terms of the compound of the present invention per 10,000 m². Whenthe pest control agent of the present invention is formulated into anemulsifiable concentrate, a wettable powder, a flowable formulation andso on, the pest control agent is usually applied after diluting withwater so that the concentration of the active ingredient becomes 0.01 to10,000 ppm, and a granule or a dust is usually applied as it is.

These formulations or water dilutions of the formulations may bedirectly sprayed over pests or plants such as crop plants to beprotected from pests, or may be used in the soil treatment for thecontrol of pests which inhabit the soil of the cultivated land.

Application can also be conducted by a method of directly winding theresin formulation formed into sheet-shaped, or string- or cord-shapedformulation around plants, disposing the formulation in the neighborhoodof plants, or spreading the formulation on the soil surface at the root.

The compound of the present invention can be used as a pest controlagent in cultivating field such as farm, paddy field, lawn or orchard,or non-cultivating field. The compound of the present invention cancontrol pests inhabiting the cultivating field in the cultivating fieldwhere the following “plant crops” are cultivated.

Agricultural crops: corn, rice, wheat, barley, rye, oat, sorghum,cotton, soybean, peanut, sarrazin, sugar beet, rapeseed, sunflower,sugar cane, tobacco, etc.;

Vegetables: Solanaceae vegetables (eggplant, tomato, green pepper, hotpepper, potato etc.), Cucurbitaceae vegetables (cucumber, pumpkin,zucchini, watermelon, melon etc.), Cruciferae vegetables (Japaneseradish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, brownmustard, broccoli, cauliflower etc.), Compositae vegetables (burdock,garland chrysanthemum, artichoke, lettuce etc.), Liliaceae vegetables(Welsh onion, onion, garlic, asparagus etc.), Umbelliferae vegetables(carrot, parsley, celery, parsnip etc.), Chenopodiaceae vegetables(spinach, Swiss chard etc.), Labiatae vegetables (Japanese basil, mint,basil etc.), strawberry, sweat potato, yam, aroid, etc.;

Fruit trees: pomaceous fruits (apple, common pear, Japanese pear,Chinese quince, quince etc.), stone fleshy fruits (peach, plum,nectarine, Japanese plum, cherry, apricot, prune etc.), citrus plants(Satsuma mandarin, orange, lemon, lime, grapefruit etc.), nuts(chestnut, walnut, hazel nut, almond, pistachio, cashew nut, macadamianut etc.), berry fruits (blueberry, cranberry, blackberry, raspberryetc.), grape, persimmon, olive, loquat, banana, coffee, date, coconutpalm, oil palm, etc.;

Trees other than fruit trees: tea, mulberry, woody plants (azalea,camellia, hydrangea, sasanqua, Illicium religiosum, cherry tree, tuliptree, crape myrtle, fragrant olive etc.), street trees (ash tree, birch,dogwood, eucalyptus, ginkgo, lilac, maple tree, oak, poplar, cercis,Chinese sweet gum, plane tree, zelkova, Japanese arborvitae, fir tree,Japanese hemlock, needle juniper, pine, spruce, yew, elm, horse-chestnutetc.), sweet viburnum, Podocarpus macrophyllus, Japanese cedar, Japanesecypress, croton, spindle tree, Chainese howthorn, etc.

Lawn: zoysia (Japanese lawn grass, mascarene grass, etc.), Bermuda grass(Cynodon dactylon, etc.), bent grass (creeping bent grass, Agrostisstolonifera, Agrostis tenuis, etc.), bluegrass (Kentucky bluegrass,rough bluegrass, etc.), fescue (tall fescue, chewing fescue, creepingfescue, etc.), ryegrass (darnel, perennial ryegrass, etc.), cocksfoot,timothy grass, etc.;

Others: flowers (rose, carnation, chrysanthemum, Eustoma grandiflorumShinners (prairie gentian), gypsophila, gerbera, pot marigold, salvia,petunia, verbena, tulip, aster, gentian, lily, pansy, cyclamen, orchid,lily of the valley, lavender, stock, ornamental kale, primula,poinsettia, gladiolus, cattleya, daisy, verbena, cymbidium, begonia,etc.), bio-fuel plants (Jatropha, safflower, gold-of-pleasure,switchgrass, Miscanthus, ribbon grass, giant reed, kenaf, cassava,willow, etc.), foliage plant; etc.

The above “plant crops” include gene transgenic plant crops.

The compound of the present invention can be mixed with or can be usedin combination with other insecticide, acaricide, nematocide, soil pestcontrol agent, fungicide, herbicide, plant growth regulating agent,repellent, synergist, fertilizer, or soil modifier.

Examples of active ingredient of such the insecticide and acaricideinclude:

(1) Synthetic Pyrethroid Compounds:

acrinathrin, allethrin, beta-cyfluthrin, bifenthrin, cycloprothrin,cyfluthrin, cyhalothrin, cypermethrin, empenthrin, deltamethrin,esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, flucythrinate,flufenoprox, flumethrin, fluvalinate, halfenprox, imiprothrin,permethrin, prallethrin, pyrethrins, resmethrin, sigma-cypermethrin,silafluofen, tefluthrin, tralomethrin, transfluthrin, tetramethrin,phenothrin, cyphenothrin, alpha-cypermethrin, zeta-cypermethrin,lambda-cyhalothrin, gamma-cyhalothrin, furamethrin, tau-fluvalinate,metofluthrin,2,3,5,6-tetrafluoro-4-methylbenzyl=2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate,2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl=2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate,2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl=2,2,3,3-tetramethylcyclopropanecarboxylate, and so on;

(2) Organic Phosphorous Compounds:

acephate, Aluminium phosphide, butathiofos, cadusafos, chlorethoxyfos,chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanophos: CYAP,diazinon, DCIP (dichlorodiisopropyl ether), dichlofenthion:ECP,dichlorvos:DDVP, dimethoate, dimethylvinphos, disulfoton, EPN, ethion,ethoprophos, etrimfos, fenthion:MPP, fenitrothion:MEP, fosthiazate,formothion, Hydrogen phosphide, isofenphos, isoxathion, malathion,mesulfenfos, methidathion:DMTP, monocrotophos, naled:BRP,oxydeprofos:ESP, parathion, phosalone, phosmet:PMP, pirimiphos-methyl,pyridafenthion, quinalphos, phenthoate:PAP, profenofos, propaphos,prothiofos, pyraclorfos, salithion, sulprofos, tebupirimfos, temephos,tetrachlorvinphos, terbufos, thiometon, trichlorphon:DEP, vamidothion,phorate, cadusafos, and so on;

(3) Carbamate Compounds:

alanycarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran,carbosulfan, cloethocarb, ethiofencarb, fenobucarb, fenothiocarb,fenoxycarb, furathiocarb, isoprocarb:MIPC, metolcarb, methomyl,methiocarb, NAC, oxamyl, pirimicarb, propoxur:PHC, XMC, thiodicarb,xylylcarb, aldicarb, and so on;

(4) Nereistoxin Compounds:

cartap, bensultap, thiocyclam, monosultap, bisultap, and so on;

(5) Neonicotinoid Compounds:

imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid,dinotefuran, clothianidin, and so on;

(6) Benzoylurea Compounds:

chlorfluazuron, bistrifluoron, diafenthiuron, diflubenzuron, fluazuron,flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron, teflubenzuron, triflumuron, triazuron, and so on;

(7) Phenylpyrazole Compounds:

acetoprole, ethiprole, fipronil, vaniliprole, pyriprole, pyrafluprole,and so on;

(8) Bt Toxin Insecticides:

Live spores derived from and crystal toxins produced from Bacillusthuringiesis and a mixture thereof;

(9) Hydrazine Compounds:

chromafenozide, halofenozide, methoxyfenozide, tebufenozide, and so on;

(10) Organic Chlorine Compound:

aldrin, dieldrin, dienochlor, endosulfan, methoxychlor, and so on;

(11) Natural Insecticides:

machine oil, nicotine-sulfate;

(12) Other Insecticides:

avermectin-B, bromopropylate, buprofezin, chlorphenapyr, cyromazine,D-D(1,3-Dichloropropene), emamectin-benzoate, fenazaquin, flupyrazofos,hydroprene, methoprene, indoxacarb, metoxadiazone, milbemycin-A,pymetrozine, pyridalyl, pyriproxyfen, spinosad, sulfluramid,tolfenpyrad, triazamate, flubendiamide, lepimectin, Arsenic acid,benclothiaz, Calcium cyanamide, Calcium polysulfide, chlordane, DDT,DSP, flufenerim, flonicamid, flurimfen, formetanate, metam-ammonium,metam-sodium, Methyl bromide, Potassium oleate, protrifenbute,spiromesifen, Sulfur, metaflumizone, spirotetramat, pyrifluquinazone,spinetoram, chlorantraniliprole, tralopyril, and so on.

Examples of the active ingredient of the repellent includeN,N-diethyl-m-toluamide, limonene, linalool, citronellal, menthol,menthone, hinokitiol, geraniol, eucalyptol, indoxacarb, carane-3,4-diol,MGK-R-326, MGK-R-874 and BAY-KBR-3023.

Examples of the active ingredient of the synergist include5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxol,N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylmide,octachlorodipropylether, thiocyanoacetic acidisobornyl,N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo[2.2.2]oct-5-ene-2,3-dicarboxylmide.

EXAMPLES

Hereinafter, the present invention will be described in more detail byway of Production Examples, Formulation Examples and Test Examples, butthe present invention is not limited thereto.

First, Production Examples of the compound of the present invention willbe described.

Production Example 1

To a chloroform solution (10 mL) of3-hydroxymethyl-1-(2-propynyl)imidazolidine-2,4-dione (450 mg, 2.68mmol) and(1R)-trans-3-[(1Z)-2-cyano-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylicacid (478 mg, 2.50 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride (516 mg, 2.70 mmol) and 4-dimethylaminopyridine (15 mg)were added. After stirring at room temperature for 3 hours, water waspoured into the reaction solution and the solution was extracted withethyl acetate. The organic layer was dried over magnesium sulfate andthen concentrated under reduced pressure condition, and the residue wassubjected to silica gel column chromatography to obtain 240 mg of2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl=(1R)-trans-3-[(1Z)-2-cyano-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the present invention compound(1)) represented by the following formula:

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.22 (s, 3H), 1.36 (s,3H), 1.79 (d, 1H, J=5.3 Hz), 2.37 (t, 1H, J=2.5 Hz), 2.54 (dd, 1H,J=9.5, 5.3 Hz), 4.06 (s, 2H), 4.27 (d, 2H, J=2.5 Hz), 5.31 (d, 1H,J=10.4 Hz), 5.52 (d, 1H, J=10.4 Hz), 5.60 (dd, 2H), 5.94 (d, 1H, J=10.4Hz), 6.24 (dd, 1H, J=10.4 Hz, 17.2 Hz)

Production Example 2

3-hydroxymethyl-1-(2-propynyl)imidazolidine-2,4-dione (450 mg, 2.68mmol) vas dissolved in tetrahydrofuran (10 mL), and 0.35 mL of pyridinewas added. To the mixed solution, a tetrahydrofuran solution (5 mL) of(1R)-trans-3-[(1Z,3E)-2-cyano-1,3-pentadienyl]-2,2-dimethylcyclopropanecarboxylicacid chloride (599 mg, 2.68 mmol) was added under ice cooling. Afterstirring at room temperature for 12 hours, water was poured into thereaction solution and the solution was extracted with ethyl acetate. Theorganic layer was washed in turn with 5% hydrochloric acid, saturatedsodium bicarbonate water and saturated brine, and then dried overmagnesium sulfate. After concentration under reduced pressure condition,the residue was subjected to silica gel column chromatography to obtain771 mg of2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl=(1R)-trans-3-[(1Z,3E)-2-cyano-1,3-pentadienyl]-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the present invention compound(2)) represented by the following formula:

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (s, 3H), 1.34 (s,3H), 1.74 (d, 1H, J=5.6 Hz), 1.83 (d, 3H, J=6.8 Hz), 2.37 (t, 1H, J=2.5Hz), 2.50 (dd, 1H, J=9.5, 5.3 Hz), 4.06 (s, 2H), 4.27 (d, 2H, J=2.5 Hz),5.51 (d, 1H, J=10.4 Hz), 5.59 (d, 1H, J=10.4 Hz), 5.78 (d, 1H), 5.95 (d,1H), 6.10 (dd, 1H)

Specific examples of the compound of the present invention will bedescribed below.

2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl=(1R)-trans-3-[(1Z)-2-cyano-4-methyl-1,3-pentadienyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl=(1R)-trans-3-[(1Z)-2-cyano-3-methyl-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

Reference Production Examples will be described below with respect tothe production of the carboxylic acid compound (3).

Reference Production Example 1

Methyl-(1R)-trans-3-formyl-2,2-dimethylcyclopropane carboxylate (2.53 g,16.2 mmol), 3-pentenonitrile (1.90 g, 23.5 mmol) and anhydrous potassiumcarbonate (3.22 g, 23.3 mmol) were added to 30 mL ofN,N-dimethylformamide and the mixture was stirred at room temperaturefor 24 hours. The reaction solution was added to 100 mL of ice water andthe solution was extracted twice with each 100 mL of ethyl acetate. Theobtained ethyl acetate layers were combined, washed once with 50 mL ofsaturated brine and then dried over magnesium sulfate. Afterconcentration under reduced pressure condition, the residue wassubjected to silica gel column chromatography to obtain 0.94 g ofmethyl-(1R)-trans-3-[(1Z,3E)-2-cyano-1,3-pentadienyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.22 (s, 3H), 1.35 (s,3H), 1.75 (d, 1H, J=5.2 Hz), 1.82 (d, 3H, J=5.2 Hz), 2.5 (m, 1H, J=10.0,5.2 Hz), 3.7 (s, 3H), 5.82 (d, 1H, J=10.0 Hz), 5.96 (d, 1H, J=16.8 Hz),6.10 (m, 1H)

Reference Production Example 2

Methyl=(1R)-trans-3-[(1Z,3E)-2-cyano-1,3-pentadienyl]-2,2-dimethylcyclopropanecarboxylate (502 mg, 2.29 mmol) was dissolved in a mixed liquid of 3 mLof methanol and 1 mL of water, and then potassium hydroxide (300 mg,5.36 mmol) was added and the mixed solution was stirred at roomtemperature for 24 hours. The reaction solution was added to 20 mL ofice water and the solution was extracted with 20 mL of ethyl acetate. Tothe obtained aqueous layer, 5% hydrochloric acid was added until the pHbecame 2, and then the solution was extracted with 30 mL of ethylacetate. The ethyl acetate layer was washed twice with 20 mL ofsaturated brine and then dried over magnesium sulfate. Afterconcentration under reduced pressure condition, 452 mg of(1R)-trans-3-[(1Z,3E)-2-cyano-1,3-pentadienyl]-2,2-dimethylcyclopropanecarboxylicacid represented by the following formula:

was obtained.

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.23 (s, 3H), 1.38 (s,3H), 1.76 (d, 1H, J=5.2 Hz), 1.82 (d, 3H, J=6.4 Hz), 2.54 (dd, 1H,J=10.0, 5.2 Hz), 5.82 (d, 1H, J=10.0 Hz), 5.97 (d, 1H, J=15.6 Hz), 6.11(m, 1H)

Reference Production Example 3

Methyl=(1R)-trans-3-formyl-2,2-dimethylcyclopropane carboxylate (2.53 g,16.2 mmol), 3-butenonitrile (3.62 g, 54.0 mmol) and anhydrous potassiumcarbonate (3.22 g, 23.3 mmol) were added to 30 mL ofN,N-dimethylformamide and the mixture was stirred at room temperaturefor 24 hours. The reaction solution was added to 100 mL of ice water andthe solution was extracted twice with each 100 mL of ethyl acetate. Theethyl acetate layers were combined, washed once with 50 mL of saturatedbrine and then dried over magnesium sulfate. After concentration underreduced pressure condition, the residue was subjected to silica gelcolumn chromatography to obtain 0.37 g ofmethyl=(1R)-trans-3-[(1Z)-2-cyano-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.24 (s, 3H), 1.35 (s,3H), 1.81 (d, 1H, J=5.2 Hz), 2.54 (dd, 1H, J=10.4, 5.2 Hz), 3.71 (s,3H), 5.30 (d, 1H, J=10.8 Hz), 5.61 (d, 1H, J=17.2 Hz), 5.98 (d, 1H, 10.4Hz), 6.26 (dd, 1H, J=10.4, 17.2 Hz)

Reference Production Example 4

Methyl=(1R)-trans-3-[(1Z)-2-cyano-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylate (483 mg, 2.36 mmol) was dissolved in a mixed liquid of 3 mLof tetrahydrofuran and 1 mL of water, and then potassium hydroxide (215mg, 3.84 mmol) was added and the solution was stirred at roomtemperature for 24 hours. The reaction solution was added to 20 mL ofice water, and the solution was extracted with 20 mL of ethyl acetate.To the obtained aqueous layer, 5% hydrochloric acid was added until thepH became 2, and then the solution was extracted with 30 mL of ethylacetate. The ethyl acetate layer washed twice with 20 mL of saturatedbrine and then dried over magnesium sulfate. After concentration underreduced pressure condition, 440 mg of(1R)-trans-3-[(1Z)-2-cyano-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylicacid represented by following formula:

was obtained.

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.25 (s, 3H), 1.38 (s,3H), 1.82 (d, 1H, J=5.2 Hz), 2.56 (dd, 1H, J=10.4, 5.2 Hz), 5.32 (d, 1H,J=10.8 Hz), 5.62 (d, 1H, J=17.2 Hz), 6.01 (d, 1H, 10.4 Hz), 6.25 (dd,1H, J=10.4, 17.2 Hz)

Reference Production Example 5

(1R)-trans-3-[(1Z)-2-cyano-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylicacid (440 mg, 2.30 mmol) was dissolved in 3 mL of tetrahydrofuran andthen thionyl chloride (301 mg, 2.53 mmol) and 10 mg ofN,N-dimethylformamide were added and the solution was stirred at roomtemperature for 1 hours, and further at 60° C. of 3 hours. The reactionsolution was concentrated under reduced pressure condition to obtain 460mg of(1R)-trans-3-[(1Z)-2-cyano-1,3-butadienyl]-2,2-dimethylcyclopropanecarboxylicacid chloride represented by the following formula:

as a pale yellow liquid.

Formulation Examples are shown below. Parts are by mass.

Formulation Example 1

Twenty (20) parts of each of the compounds (1) to (2) of the presentinvention is dissolved in 65 parts of xylene and 15 parts of SOLPOL3005X (a registered trademark of TOHO Chemical Industry Co., Ltd.) isadded thereto and thoroughly mixed with stirring to obtain emulsifiableconcentrates.

Formulation Example 2

Five (5) parts of SORPOL 3005X is added to 40 parts of each of thecompounds (1) to (2) of the present invention and the mixture isthoroughly mixed, and 32 parts of CARPLEX #80 (synthetic hydratedsilicon oxide, a registered trademark of SHIONOGI & CO., LTD.) and 23parts of 300-mesh diatomaceous earth are added thereto, followed bymixing with stirring by a mixer to obtain wettable powders.

Formulation Example 3

A mixture of 1.5 parts of each of the compounds (1) to (2) of thepresent invention, 1 part of TOKUSIL GUN (synthetic hydrated siliconoxide, manufactured by Tokuyama Corporation), 2 parts of REAX 85A(sodium lignin sulfonate, manufactured by West Vaco Chemicals), 30 partsof BENTONITE FUJI (bentonite, manufactured by Houjun) and 65.5 parts ofSHOUKOUZAN A clay (kaoline clay, manufactured by Shoukouzan Kougyousho)is thoroughly pulverized and mixed, and water is added thereto. Themixture is thoroughly kneaded, granulated by an extruding granulator,and then dried to obtain 1.5% granules.

Formulation Example 4

To a mixture of 10 parts of each of the compounds (1) to (2) of thepresent invention, 10 parts of phenylxylylethane and 0.5 part of SUMIDURL-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer UrethaneCo., Ltd.) is added 20 parts of 10% aqueous solution of gum arabic, andthe mixture is stirred with a homomixer to obtain an emulsion having anaverage particle diameter of 20 μm. To the emulsion, 2 parts of ethyleneglycol is added and the mixture is further stirred in a warm bath at atemperature of 60° C. for 24 hours to obtain microcapsule slurry. On theother hand, 0.2 part of xanthan gum and 1.0 part of VEEGUM R (aluminummagnesium silicate, manufactured by Sanyo Chemical Industries, Ltd.) aredispersed in 56.3 parts of ion-exchanged water to obtain a thickenersolution. Then, 42.5 parts of the above-mentioned microcapsule slurryand 57.5 parts of the above-mentioned thickener solution are mixed toobtain microcapsules.

Formulation Example 5

A mixture of 10 parts of each of the compounds (1) to (2) of the presentinvention and 10 parts of phenylxylylethane is added to 20 parts of a10% aqueous solution of polyethylene glycol, and the mixture is stirredby a homomixer to obtain an emulsion having an average particle diameterof 3 μm. On the other hand, 0.2 part of xanthan gum and 1.0 part ofVEEGUM R (aluminum magnesium silicate, manufactured by Sanyo ChemicalIndustries, Ltd.) are dispersed in 58.8 parts of ion-exchanged water toobtain a thickener solution. Then, 40 parts of the above-mentionedemulsion solution and 60 parts of the above-mentioned thickener solutionare mixed to obtain flowable formulations.

Formulation Example 6

To 5 parts of each of the compounds (1) to (2) of the present invention,3 parts of CARPLEX #80 (synthetic hydrated silicon oxide, a registeredtrademark of SHIONOGI & CO., LTD.), 0.3 part of PAP (a mixture ofmonoisopropyl phosphate and diisopropyl phosphate) and 91.7 parts oftalc (300 mesh) are added and the mixture is stirred by a mixer toobtain dusts.

Formulation Example 7

Zero point one (0.1) part of each of the compounds (1) to (2) of thepresent invention is dissolved in 10 parts of dichloromethane and thesolution is mixed with 89.9 parts of deodorized kerosine to obtain oilsolutions.

Formulation Example 8

Zero point one (0.1) part of each of the compounds (1) to (2) of thepresent invention and 39.9 parts of deodorized kerosine are mixed anddissolved, and the solution is filled into an aerosol container and avalve portion is installed. Then, 60 parts of power propellant(liquefied petroleum gas) is filled therein under pressure through thevalve portion to obtain oil-based aerosol formulations.

Formulation Example 9

Zero point six (0.6) part of each of the compounds (1) to (2) of thepresent invention, 5 parts of xylene, 3.4 parts of deodorized kerosineand 1 part of Reodol MO-60 (emulsifier, a registered trademark of KaoCorporation) are mixed and dissolved, and the solution and 50 parts ofwater are filled into an aerosol container, and then 40 parts of powerpropellant (liquefied petroleum gas) is filled therein under pressurethrough a valve portion to obtain aqueous aerosol formulations.

Formulation Example 10

Zero point three (0.3) g of each of the compounds (1) to (2) of thepresent invention is dissolved in 20 ml of acetone and the solution isuniformly mixed with stirring with 99.7 g of a base material for a coil(obtained by mixing Tabu powder, Pyrethrum marc and wooden powder at aratio of 4:3:3). Then, 100 ml of water is added thereto, and the mixtureis thoroughly kneaded, dried and molded to obtain insecticidal coils.

Formulation Example 11

A mixture of 0.8 g of each of the compounds (1) to (2) of the presentinvention and 0.4 g of piperonyl butoxide is dissolved in acetone andthe total volume is adjusted to 10 ml. Then, 0.5 ml of this solution isuniformly impregnated into a base material for an insecticidal mat forelectric heating (a plate obtained by hardening fibrils of a mixture ofcotton linters and pulp) having a size of 2.5 cm×1.5 cm and a thicknessof 0.3 cm to obtain insecticidal mats for electric heating.

Formulation Example 12

A solution obtained by dissolving 3 parts of each of the compound (1) to(2) of the present invention in 97 parts of deodorized kerosine ispoured into a vessel made of vinyl chloride. A liquid absorptive corewhose upper part can be heated by a heater (an inorganic pulverizedpowder is hardened with a binder and sintered) is inserted thereinto toobtain parts to be used for a liquid absorptive core type thermaltranspiring apparatus.

Formulation Example 13

One hundred (100) mg of each of the compound (1) to (2) of the presentinvention is dissolved in an appropriate amount of acetone and thesolution is impregnated into a porous ceramic plate having a size of 4.0cm×4.0 cm and a thickness of 1.2 cm to obtain thermal fumigants.

Formulation Example 14

One hundred (100) μg of each of the compound (1) to (2) of the presentinvention is dissolved in an appropriate amount of acetone and thesolution is uniformly applied to filter paper having a size of 2 cm×2 cmand a thickness of 0.3 mm, and air-dried to remove acetone, and thusvolatile agents for using at room temperature are obtained.

Formulation Example 15

Ten (10) parts of each of the compound of the present inventions (1) to(2), 35 parts of white carbon containing 50 parts of a polyoxyethylenealkyl ether sulfate ammonium salt, and 55 parts of water are mixed andthen finely ground by a wet grinding method to obtain 10% formulations.

Next, it will be demonstrated by Test Examples that the compound of thepresent invention is effective as an active ingredient of a pestcontrolling agent.

Test Example 1

Each of the present invention compounds (1) and (2) (0.00156 parts)produced in the aforementioned Production Examples was dissolved in 10parts of dichloromethane and the resulting solution was mixed with89.99844 parts of deodorized kerosine to prepare a 0.00156% (w/v) oilsolution.

Ten German cockroaches (5 of each male and female) were released in atest container (measuring 8.75 cm in diameter and 7.5 cm in height,bottom area covered with a 16 mesh wire netting) coated with butter atan inner wall, and the container was disposed on the bottom of a testchamber (bottom surface measuring 46 cm and 46 cm, 70 cm in height).

From 60 cm in height above the container, 1.5 ml of the oil solution ofeach of the present invention compounds (1) and (2) was sprayed using aspray gun (spray pressure: 0.4 kg/cm²). Thirty seconds after spraying,the container was removed from the test chamber. After a given time, thenumber of knockdowned cockroaches was counted and a knockdown rate wasdetermined (repeated twice). The knockdown rate was calculated by thefollowing equation.Knockdown rate (%)=(number of knockdowned cockroaches/number of testcockroaches)×100

For comparison, a test was carried out in the same manner as describedabove, except that2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl=(1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound described in “Pestiside Science”, 1979, 10, p.291, hereinafter referred to as the comparative compound (1))represented by the following formula:

and2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl=(1R)-trans-3-[(1E)-2-methyl-1-butadienyl)-2,2-dimethylcyclopropanecarboxylate (compound described in JP-A-49-11854, hereinafter referredto as the comparative compound (2)) represented by the followingformula:

were used.

The results after 2 minutes are shown in Table 1.

TABLE 1 Knockdown rate (%) Test compounds after 2 minutes Presentinvention compound (1) 95 Present invention compound (2) 100 Comparativecompound (1) 45 comparative compound (2) 10

INDUSTRIAL APPLICABILITY

The compound of the present invention has an excellent pest controleffect and is therefore useful as an active ingredient of a pest controlagent.

The invention claimed is:
 1. An ester compound represented by formula(1):

wherein R³ represents hydrogen or methyl, R⁴ represents hydrogen orC1-C4 alkyl, and R⁵ represents hydrogen or C1-C4 alkyl.
 2. The estercompound according to claim 1, wherein a relative configuration of thesubstituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration in formula (1).
 3. The ester compound according to claim1, wherein an absolute configuration of the 1-position of thecyclopropane ring is an R configuration in formula (1).
 4. The estercompound according to claim 1, wherein an absolute configuration of the1-position of the cyclopropane ring is an R configuration, and arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration in formula (1).
 5. The estercompound according to claim 1, wherein a relative configuration of thesubstituent of the 1′-position existing on the substituent at the3-position of the cyclopropane ring is Z-configuration in formula (1).6. The ester compound according to claim 1, wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration and a relative configuration of the substituent of the1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration in formula (1).
 7. The estercompound according to claim 1, wherein an absolute configuration of the1-position of the cyclopropane ring is an R configuration, a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration, and a relative configuration of the substituent ofthe 1′-position existing on the substituent at the 3-position of thecyclopropane ring is Z-configuration in formula (1).
 8. The estercompound according to claim 1, wherein R³ is hydrogen in formula (1). 9.The ester compound according to claim 1, wherein R⁴ is hydrogen ormethyl in formula (1).
 10. The ester compound according to claim 1,wherein R⁴ is hydrogen in formula (1).
 11. The ester compound accordingto claim 1, wherein R⁴ is methyl in formula (1).
 12. The ester compoundaccording to claim 1, wherein R⁵ is hydrogen in formula (1).
 13. Theester compound according to claim 1, wherein R³ is hydrogen and R⁴ ishydrogen or methyl in formula (1).
 14. The ester compound according toclaim 1, wherein R³ is hydrogen and R⁴ is hydrogen in formula (1). 15.The ester compound according to claim 1, wherein R³ is hydrogen and R⁴is methyl in formula (1).
 16. The ester compound according to claim 1,wherein R³ is hydrogen and R⁵ is hydrogen in formula (1).
 17. The estercompound according to claim 1, wherein R⁴ is hydrogen or methyl, and R⁵is hydrogen in formula (1).
 18. The ester compound according to claim 1,wherein R⁴ is hydrogen and R³ is hydrogen in formula (1).
 19. The estercompound according to claim 1, wherein R⁴ is methyl and R⁵ is hydrogenin formula (1).
 20. The ester compound according to claim 1, wherein R³is hydrogen, R⁴ is hydrogen or methyl, and R⁵ is hydrogen in formula(1).
 21. The ester compound according to claim 1, wherein R³ ishydrogen, R⁴ is hydrogen, and R⁵ is hydrogen in formula (1).
 22. Theester compound according to claim 1, wherein R³ is hydrogen, R⁴ ismethyl, and R⁵ is hydrogen in formula (1).
 23. A pest control agentcomprising the ester compound according to claim 1 and an inert carrier.24. A method of controlling pests, which comprises a step of applying aneffective amount of the ester compound according to claim 1 to pests ora place where pests habitat.
 25. A method of controlling pests, whichcomprises the step of applying an effective amount of the ester compoundaccording to claim 1 to cockroaches or a place where cockroachesinhabits.
 26. The method of controlling pests according to claim 25,wherein the cockroach is American cockroach (Periplaneta Americana). 27.The method of controlling pests according to claim 25, wherein thecockroach is German cockroach (Blattella germanica).
 28. A method ofcontrolling pests, which comprises a step of spraying an effectiveamount of the ester compound according to claim 1 to cockroaches or aplace where cockroaches inhabit.
 29. The method of controlling pestsaccording to claim 28, wherein the cockroach is American cockroach(Periplaneta Americana).
 30. The method of controlling pests accordingto claim 28, wherein the cockroach is German cockroach (Blattellagermanica).